US6821692B1 - Kind of thin films for microsystem technology and microstructuring and their use - Google Patents

Kind of thin films for microsystem technology and microstructuring and their use Download PDF

Info

Publication number
US6821692B1
US6821692B1 US09/230,975 US23097599A US6821692B1 US 6821692 B1 US6821692 B1 US 6821692B1 US 23097599 A US23097599 A US 23097599A US 6821692 B1 US6821692 B1 US 6821692B1
Authority
US
United States
Prior art keywords
biopolymer
layer
thin layer
gelatin
enzymatically degradable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/230,975
Inventor
Eugen Ermantraut
Johann Michael Köhler
Torsten Schulz
Klaus Wohlfart
Stefan Wölfl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clondiag Chip Technologies GmbH
Original Assignee
Clondiag Chip Technologies GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19634120A external-priority patent/DE19634120A1/en
Application filed by Clondiag Chip Technologies GmbH filed Critical Clondiag Chip Technologies GmbH
Assigned to CLONDIAG CHIP TECHNOLOGIES GMBH reassignment CLONDIAG CHIP TECHNOLOGIES GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ERMANTRAUT, EUGEN, KOEHLER, JOHANN MICHAEL, SCHULZ, TORSTEN, WOELFL, STEFAN, WOHLFART, KLAUS
Application granted granted Critical
Publication of US6821692B1 publication Critical patent/US6821692B1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12QMEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/001Enzyme electrodes
    • C12Q1/002Electrode membranes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312Organic layers, e.g. photoresist
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277Apparatus
    • B01J2219/00497Features relating to the solid phase supports
    • B01J2219/00527Sheets
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Definitions

  • the present invention relates to novel thin layers for microsystem techniques and microstructuring which may be employed within the range of such technologies in various manners.
  • the thin layers heretofore employed according to the state of art in the microsystem technique and in microstructuring, as for example for manufacturing membranes, sandwiched system contacts and circuits are based on the use of inorganic layers, such as layers of SiO 2 , Si 3 N 4 , and Al 2 O 3 frequently employed, and metal layers and metal layer systems, respectively.
  • Poisonous chemicals and such being harmful to health as for example strong acids, alkalies, and oxidants, are employed to produce the desired structures, or extremely expensive processes, such as reactive ion etching and plasma etching, respectively, are required therefor (refer to S. Büittgenbach, Mikromechanik, B. G. Teubner, Stuttgart, 1994).
  • the only organic layers which are to be used in structuring processes are photoresists which after the desired structure being imparted to the layer to be structurized are removed, as a rule.
  • biopolymer films also within the range of thickness relevant for the thin layer techniques of from 30 nm to 3 ⁇ m to satisfy very high quality standards.
  • certain dyestuffs or photoactivatable groups effect a cross-linking of the biopolymer layer subsequent to a photochemical activation so that their enzymatic decomposition rate considerably slows down compared to unexposed layer ranges.
  • the layer thicknesses are reproducible within a range of a few 10 nm from solutions with a solids content from 1 to 30% by spin coating which itself is known. Layers applied in such a manner are even in such an extremely thin layer range unexpectedly homogeneous and free of defects. They also resist tempering steps of up to 250° C. without any problems and without any signs of degradation during the further process of microstructuring.
  • a hydrosoluble gelatin changes to a water-insoluble material after a cross-linkage in that molecules are enclosed therein or, alternatively, are bound thereto covalently or non-covalently.
  • the proposed thin layers in the field of application concerned, can be used to various ends.
  • the entire sandwich assembly is inserted into a receptacle containing an enzymic bath.
  • the enzymic bath preferably consists of a protease K-buffer substantially constituted of 10% SDS, 10 mM NaCl, 10 mM EDTA and Tris-HCl, and to which 10 mg/ml protease K is added.
  • the pH-value of said bath is set to 8.5.
  • a gelatin layer of about 200 nm thickness is entirely degraded at ambient temperature within about 8 h.
  • the biopolymer layer was used as a sacrificial layer for generating a self-supporting novolac structure.
  • diazo-naphthoquinone which is in AZ-photoresists a usual photosensitive component, binds to OH-groups of the gelatin and, hence, inhibits a protease applied in a buffer solution of being degraded.
  • diazo-naphthoquinone is converted into a carboxyl acid which is salified and separated from the gelatin. At such locations the degradation can take place uninhibited.
  • di-acidostilbene being dissolved in water and having its maximum sensitivity at about 345 nm, is employed as a photoactive component with a spectral sensitivity in the visible or in the ultraviolet spectral range, wherein a sodium salt of 4,4-di-acidostilbene-2,2-sulpho acid which has been dissolved in water at a mixing ratio of from 1:50 to 1:100 has proven as particularly advantageous.
  • a solid gelatin for example Quality Bloom 60 made of pigskin is added to the aqueous di-acidostilbene solution at a quantity ratio of from 10:1 to 100:1, depending on the desired degree of cross-linking in the biopolymeric layer to be produced. In the present example, about 40 mg gelatin per ml.
  • di-acidostilbene solution are added. After the gelatin has dissolved the solution is filtered through a microfilter to 200 nm. The solution obtained in this way is spun onto a substrate, for example, consisting of a metal, a polymer, silicon, coated silicon or glass, as common use in microlithography. In this manner according to the present example a plane homogeneous gelatin layer having a thickness of about 100 nm is formed on a silicon substrate. The thin layer is provided with a mask adapted to a subsequent and desired structure and is subjected to an UV-exposure at a wavelength of 360 nm for about 400 s.
  • the degradation rates obtainable in the present example lie at about 20-30 nm/min. According to the manner described hereinabove, it is feasible to produce sizes of structures down to 1 ⁇ m.
  • biopolymers to provide defined functions for covalent but also non-covalent coupling to further molecules (so, for example, it is feasible to couple to a gelatin layer by way of amino-, carboxy-, hydroxy-and thio-functions but also by way of hydrogen bridge linkage), can be particularly advantageously exploited in thin layer structures suitably structurized and generated according to the above specifications for a special application, as will be described in the following.
  • Local reaction spaces are defined by way of structurized gelatin pads. Due to the chemical diversity of the functional groups of the collagen polymer it is feasible to bind diverse molecules after a specific activation. In other words, the same matrix can be utilized for coupling molecules having a diversity of functional groups, the expensive modification of the molecules for immobilization is omitted.

Abstract

The present invention relates to novel thin layers for microsystem techniques and microstructuring. It is an object of the invention to provide thin layers which can be manufactured under less problems and more economically than the previous conventional layers, and which permit the use of existing technologies for microstructuring. The object is realized in that the thin layer is formed of an enzymatically degradable biopolymer in a range of layer thicknesses of from 30 nm to 3 μm. Biopolymeric thin layers manufactured according to the invention permit their application, after a respective structurizing, as test assays or in setting up substance libraries.

Description

BACKGROUND OF THE INVENTION
The present invention relates to novel thin layers for microsystem techniques and microstructuring which may be employed within the range of such technologies in various manners.
The thin layers heretofore employed according to the state of art in the microsystem technique and in microstructuring, as for example for manufacturing membranes, sandwiched system contacts and circuits are based on the use of inorganic layers, such as layers of SiO2, Si3N4, and Al2O3 frequently employed, and metal layers and metal layer systems, respectively. Poisonous chemicals and such being harmful to health, as for example strong acids, alkalies, and oxidants, are employed to produce the desired structures, or extremely expensive processes, such as reactive ion etching and plasma etching, respectively, are required therefor (refer to S. Büittgenbach, Mikromechanik, B. G. Teubner, Stuttgart, 1994). The only organic layers which are to be used in structuring processes are photoresists which after the desired structure being imparted to the layer to be structurized are removed, as a rule.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide thin layers which can be manufactured less critically and more economically than previous conventional thin layers under use of existing technologies in microstructuring and which are suited in a particularly advantageous manner for setting-up substance libraries.
SUMMARY OF THE INVENTION
The object is realized by the characteristic features of the first claim.
Advantageous embodiments are covered by the succeeding claims. It was found that in the field of microstructuring the masking layers capable of structurizing and employed previously to this end, such as photoresist layers, may locally affect the properties of biopolymer films, for example gelatin, agarose, dextrose, and lipid.
Furthermore, it was surprisingly found that it is feasible to produce such biopolymer films also within the range of thickness relevant for the thin layer techniques of from 30 nm to 3 μm to satisfy very high quality standards. Moreover, it was found that certain dyestuffs or photoactivatable groups effect a cross-linking of the biopolymer layer subsequent to a photochemical activation so that their enzymatic decomposition rate considerably slows down compared to unexposed layer ranges.
The layer thicknesses are reproducible within a range of a few 10 nm from solutions with a solids content from 1 to 30% by spin coating which itself is known. Layers applied in such a manner are even in such an extremely thin layer range unexpectedly homogeneous and free of defects. They also resist tempering steps of up to 250° C. without any problems and without any signs of degradation during the further process of microstructuring.
The main advantage of such layers from biopolymers, however, consists in their enzymatic degradability which results in a high specificity of degradation which generally takes place under moderate conditions, at ambience, and in solutions exhibiting a pH number preferably from 4 to 9. Basically biopolymers offer the advantage that they provide definite functions for coupling covalently, but also non-covalently further molecules and layers.
Thus, for example, it is feasible to couple to a gelatin layer by way of carboxy-, amino-, and thio-functions but also by way of hydrogen bridge linkages. Furthermore it is feasible without any problems to cross-link biopolymers (for example, by means of glutaric dialdehyde in the presence of a free keto-, amino-, or hydroxyl group), and, hence, to respectively vary the properties of the produced layer.
Thus, for example, a hydrosoluble gelatin changes to a water-insoluble material after a cross-linkage in that molecules are enclosed therein or, alternatively, are bound thereto covalently or non-covalently. Depending on their formation, the proposed thin layers, in the field of application concerned, can be used to various ends.
The following embodiments illustrate feasible applications in more detail.
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment the properties of enzymes as highly specified catalysts are utilized to generate a self-supporting novolac structure under use of a biopolymeric thin layer consisting of gelatin. To this end a gelatin layer of about 200 nm thickness is applied to a cleaned silicon wafer by spin-coating. In the present example, said layer is formed by gelatin (10% v/v) dissolved in water to which 5% glutaric dialdehyde is added. Said layer is not water-soluble and is resistant to conventional photoresist coating developers. A photo reversal resist as commonly on sale is applied to said layer also by means of spin-coating. Said photoresist layer is treated according to the instructions, masked according to a desired subsequent structure, exposed, and structurized. The entire sandwich assembly is inserted into a receptacle containing an enzymic bath. Provided that gelatin is utilized for the biopolymer layer the enzymic bath preferably consists of a protease K-buffer substantially constituted of 10% SDS, 10 mM NaCl, 10 mM EDTA and Tris-HCl, and to which 10 mg/ml protease K is added. The pH-value of said bath is set to 8.5. When such an enzymic bath is employed a gelatin layer of about 200 nm thickness is entirely degraded at ambient temperature within about 8 h. In the present example, the biopolymer layer was used as a sacrificial layer for generating a self-supporting novolac structure.
In a second embodiment which again, as the foregoing first example, is based on a sandwich assembly constituted of gelatin and a photoresist, the property of enzymes as being highly specific catalysts is utilized, the functions of which are inhibited by suitable inhibitors and competitors, respectively. Accordingly, diazo-naphthoquinone, which is in AZ-photoresists a usual photosensitive component, binds to OH-groups of the gelatin and, hence, inhibits a protease applied in a buffer solution of being degraded. When exposed diazo-naphthoquinone is converted into a carboxyl acid which is salified and separated from the gelatin. At such locations the degradation can take place uninhibited. Hence, the degradation is achieved “anisotropically” in analogy to the previous selective etching techniques. At places where the inhibitor is still present the degradation speed is considerably reduced. Thus it is feasible to use biopolymers and the suitable degradation enzymes and modification enzymes, respectively, as a component of microsystem techniques as well as a mask material.
A third embodiment provides the potentiality to add a light sensitive conditioner (for example, diazo-naphthoquinone) to the biopolymeric thin layers to generate a layer which is applicable itself as a photoresist. This involves the condition that the light sensitive additive either acts as an inhibitor itself to the enzyme to be degraded or is coupled to such an inhibitor. Due to this embodiment being at one's disposal it is feasible to produce photoresists which can be developed enzymatically.
A fourth embodiment will describe the manufacturing of a lipid layer of about 100 nm thickness. To this end a solution consisting of phosphatidyl-ethanolamine in cloroform (0.1 g/ml) is spun onto a suitable substrate at 5000 revolutions per minute for 30 s.
According to a fifth embodiment it is feasible to coat a thin layer of gelatin to which is added a biogenic inhibitor of protease function, such as TFPI (tissue factor pathway inhibitor) mixed 1:1000 parts by weight, with pure gelatin. This provides for an etching stop in the case of a subsequent enzymatic treatment. In analogy thereto, a degradation stop can be incorporated in layers consisting of agarose, dextroses, and lipids by selecting a substance which exhibits an inhibiting effect to a later added enzyme.
While the foregoing embodiments are in concern of the formation of thin layers, the application of which is comparable to a known positive photoresist according to the state of art, a sixth embodiment of a thin layer according to the present invention will be described hereinafter, which compares to a negative resist.
For example, di-acidostilbene, being dissolved in water and having its maximum sensitivity at about 345 nm, is employed as a photoactive component with a spectral sensitivity in the visible or in the ultraviolet spectral range, wherein a sodium salt of 4,4-di-acidostilbene-2,2-sulpho acid which has been dissolved in water at a mixing ratio of from 1:50 to 1:100 has proven as particularly advantageous. A solid gelatin, for example Quality Bloom 60 made of pigskin is added to the aqueous di-acidostilbene solution at a quantity ratio of from 10:1 to 100:1, depending on the desired degree of cross-linking in the biopolymeric layer to be produced. In the present example, about 40 mg gelatin per ml. di-acidostilbene solution are added. After the gelatin has dissolved the solution is filtered through a microfilter to 200 nm. The solution obtained in this way is spun onto a substrate, for example, consisting of a metal, a polymer, silicon, coated silicon or glass, as common use in microlithography. In this manner according to the present example a plane homogeneous gelatin layer having a thickness of about 100 nm is formed on a silicon substrate. The thin layer is provided with a mask adapted to a subsequent and desired structure and is subjected to an UV-exposure at a wavelength of 360 nm for about 400 s. This results in the acido-groups of the diacidostilbene being photochemically split up to a bisnitrene-radical under splitting-off of nitrogen leading to a linkage of the amino-acid chains of the gelatin in the exposed ranges. The development of the exposed gelatin layer is carried out under water which results in a coarse frilling of the unexposed ranges of the gelatin layer already after 1 to 2 min. This is followed by a redevelopment in a protease buffer solution having a concentration of 0.1 mg/ml buffer-solution which, in the present example, consists of 10% sodium lauryl sulphate, 10 mM NaCl, 10 mM EDTA, Tris-HCl at an alkalescent pH-value of about 8.5.
The degradation rates obtainable in the present example lie at about 20-30 nm/min. According to the manner described hereinabove, it is feasible to produce sizes of structures down to 1 μm.
The manner of producing the cross-linking of exposed ranges according to the present invention permits the generation of even more stable structures than the respective positive structures produced by the embodiments one to five.
The advantage of biopolymers to provide defined functions for covalent but also non-covalent coupling to further molecules (so, for example, it is feasible to couple to a gelatin layer by way of amino-, carboxy-, hydroxy-and thio-functions but also by way of hydrogen bridge linkage), can be particularly advantageously exploited in thin layer structures suitably structurized and generated according to the above specifications for a special application, as will be described in the following.
It is feasible to generate regular arrays of squares on a supporting substrate in starting from a gelatin layer produced according to the foregoing specifications, imposing a mask, for example, of chessboard pattern thereupon and carrying out the exposure and development in analogy to the above described. Assuming an edge length of, for example, 16 μm for the squares then the latter have a depth of structure of 18 nm after completion of the foregoing developing process. Microstructures (pads) produced in this manner and having predetermined positions of linkage made of gelatin and allied collagens, respectively, are particularly suited for setting up screening tests and substance libraries in the field of biotechnology, molecular biology, pharmacy, and medicine. Such libraries are for finding and quickly locating interacting participants in the molecular field. It is very easy to couple proteins (for example, antibodies) or respectively modified oligonucleotides to the microstructurized gelatin pads via a peptide linkage, which enables to build up, for example, test assays.
Local reaction spaces are defined by way of structurized gelatin pads. Due to the chemical diversity of the functional groups of the collagen polymer it is feasible to bind diverse molecules after a specific activation. In other words, the same matrix can be utilized for coupling molecules having a diversity of functional groups, the expensive modification of the molecules for immobilization is omitted.

Claims (27)

What is claimed is:
1. A microstructurable thin layer consisting essentially of an enzymatically degradable biopolymer having an inhibitor or a competitor of the enzymatic degradability of said biopolymer on at least part of its surface, the thin layer having a thickness of 30 nm to 3 μm, said layer being enzymatically degradable by a suitable individual enzyme.
2. A microstructurable thin layer consisting essentially of an enzymatically degradable biopolymer intermingled with an inhibitor or a competitor of the enzymatic degradability of said biopolymer, the thin layer having a thickness of 30 nm to 3 μm, said layer being enzymatically degradable by a suitable individual enzyme.
3. A microstructurable thin layer according to claim 1 or 2, wherein the biopolymer consists of gelatin.
4. A microstructurable thin layer consisting essentially of an enzymatically degradable biopolymer consisting of agarose and having an inhibitor or a competitor on at least part of its surface, or said biopolymer intermingled with an inhibitor or a competitor, the thin layer having a thickness of 30 nm to 3 μm, said layer being enzymatically degradable by a suitable individual enzyme.
5. A microstructurable thin layer consisting essentially of an enzymatically degradable biopolymer consisting of dextrose and having an inhibitor or a competitor on at least part of its surface, or said biopolymer intermingled with an inhibitor or a competitor, the thin layer having a thickness of 30 nm to 3 μm, said layer being enzymatically degradable by a suitable individual enzyme.
6. A microstructurable thin layer consisting essentially of an enzymatically degradable biopolymer consisting of a lipid and having an inhibitor or a competitor on at least part of its surface, or said biopolymer intermingled with an inhibitor or a competitor, the thin layer having a thickness of 30 nm to 3 μm, said layer being enzymatically degradable by a suitable individual enzyme.
7. A microstructurable thin layer for microsystem technology and microstructuring consisting essentially of one degradable biopolymer enzymatically degradable by a suitable individual enzyme, the one degradable biopolymer being selected from the group consisting of gelatin, agarose, dextrose and a lipid, the biopolymer being cross-linked and combined with an inhibitor or a competitor affecting a degradation function of said individual enzyme.
8. A method for producing a structured thin layer from an enzymatically degradable biopolymeric thin layer comprising
(a) forming a biopolymeric layer comprising a biopolymer solution and a light sensitive conditioner on a substrate, said conditioner being an inhibitor of enzymatic action,
(b) exposing the biopolymeric layer to ultraviolet radiation, which causes said conditioner to be more soluble in water,
(c) separating said more soluble conditioner from the exposed biopolymeric layer, and
(d) removing the exposed biopolymeric layer by washing with an aqueous solution and an enzymatic buffer solution.
9. A method according to claim 8, in which the biopolymer consists of one selected from the group consisting of gelatin, agarose, dextrose and a lipid.
10. A method according to claim 8, in which the biopolymeric layer is applied onto the substrate by spin casting.
11. A method according to claim 10, in which the spin casting is from a solution of the biopolymer of a solids content of 1 to 30%.
12. A method according to claim 11, in which the cross-linking agent is at least one of glutaric dialdehyde and formaldehyde.
13. A method according to claim 12, in which the cross-linking agent is added to the spin casting solution in a percentage of 1 to 5%.
14. A method according to claim 9, in which the conditioner is a diazo-naphthoquinone dye, the biopolymer consists of gelatin and the enzyme in the enzymatic buffer solution is a protease.
15. A structured enzymatically degradable biopolymer thin layer produced by the method of any one of claim 8, 9, or 14.
16. A method for producing a structured thin layer from an enzymatically degradable biopolymeric thin layer comprising:
(a) forming a layer comprising a biopolymer solution, a thermally activatable cross-linking agent, and a photoactivatable radical agent for chain prolonging or linking, on a substrate thereby to form a cross-linked biopolymeric layer on the substrate,
(b) exposing the biopolymeric layer to ultraviolet radiation, and then
(c) removing unexposed biopolymeric layer by washing with an aqueous solution and an enzymatic buffer solution.
17. A method according to claim 16 in which the biopolymer consists of one selected from the group consisting of gelatin, agarose, dextrose and a lipid.
18. A method according to claim 16 or 17, in which the layer is applied onto the substrate by spin casting.
19. A method according to claim 18, in which the spin casting is from a solution of the biopolymer of a solids content of 1 to 30%.
20. A method according to claim 16, in which the cross-linking agent is at least one of glutaric dialdehyde and formaldehyde.
21. A method according to claim 19, in which the cross-linking agent is added to the spin casting solution in a percentage of 1 to 5%.
22. A method according to claim 19, in which the biopolymer consists of gelatin and the radical agent is added to the gelatin layer in such quantity that a ratio of gelatin to radical agent is 10:1 to 100:1.
23. A structured enzymatically degradable biopolymer thin layer produced by the method of claim 16.
24. A method according to claim 8, in which in (a), the biopolymer solution is applied onto the substrate and then the dye is added thereto.
25. A method according to claim 8, in which in (a), the dye is added to the biopolymer solution and then the biopolymer solution containing the dye is applied onto the substrate.
26. The method of claim 8, wherein said biopolymer is gelatin, said conditioner is a diazo-naphthoquinone dye which binds to the OH groups of the gelatin and inhibits the degradation function of a protease enzyme in a later applied buffer solution, the exposure of the biopolymer layer to ultraviolet radiation converts the diazo-naphthoquinone dye in the exposed portion of the layer to a carboxylic acid which is salified and removed from the biopolymeric layer, and the exposed portion of said layer, now free of the azo-naphthoquinone dye inhibitor, is degraded and removed by treatment with said protease enzyme buffer solution.
27. The method of claim 17 wherein said biopolymer is gelatin and the enzyme in said enzymatic buffer solution is a protease.
US09/230,975 1996-08-23 1997-08-22 Kind of thin films for microsystem technology and microstructuring and their use Expired - Fee Related US6821692B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19634120A DE19634120A1 (en) 1996-08-23 1996-08-23 Thin film for microsystem technology and microstructuring
DE19634120 1996-08-23
DE19705909 1997-02-15
DE19705909A DE19705909A1 (en) 1996-08-23 1997-02-15 Novel thin films for microsystem technology and microstructuring as well as their use
PCT/EP1997/004582 WO1998008086A1 (en) 1996-08-23 1997-08-22 New kind of thin films for microsystem technology and microstructuring and their use

Publications (1)

Publication Number Publication Date
US6821692B1 true US6821692B1 (en) 2004-11-23

Family

ID=26028675

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/230,975 Expired - Fee Related US6821692B1 (en) 1996-08-23 1997-08-22 Kind of thin films for microsystem technology and microstructuring and their use

Country Status (6)

Country Link
US (1) US6821692B1 (en)
EP (1) EP0920618B1 (en)
JP (1) JP3624382B2 (en)
AT (1) ATE313078T1 (en)
DE (2) DE19705909A1 (en)
WO (1) WO1998008086A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060244118A1 (en) * 2001-01-31 2006-11-02 Gentex Corporation High power radiation emitter device and heat dissipating package for electronic components
US20060277778A1 (en) * 2005-06-10 2006-12-14 Mick Stephen E Reusable template for creation of thin films; method of making and using template; and thin films produced from template
CN103528866A (en) * 2013-10-18 2014-01-22 江苏蓝拓生物科技有限公司 Preparation method of carbon supporting film
WO2021038058A1 (en) 2019-08-30 2021-03-04 Westfaelische Wilhelms-Universitaet Muenster Method for manufacturing a holey film, in particular for electron microscopy applications

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6797393B2 (en) 2001-11-30 2004-09-28 Eastman Kodak Company Method for making biochip substrate
JP2009207381A (en) * 2008-03-03 2009-09-17 Kaneka Corp Device for capturing monocyte

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2245009A1 (en) 1973-09-21 1975-04-18 Kodak Pathe Protein contng photo resist compsn with photoisomerisable cpd - which on exposure has greater enzyme inhibiting power
US3884703A (en) * 1972-04-17 1975-05-20 Hitachi Ltd Bisazide sensitized photoresistor composition with diacetone acrylamide
US4106938A (en) * 1977-05-23 1978-08-15 Eastman Kodak Company Vesicular composition, element and process utilizing a diol
US4251620A (en) * 1975-02-19 1981-02-17 Fuji Photo Film Co., Ltd. Light-sensitive printing plate process
US4451568A (en) * 1981-07-13 1984-05-29 Battelle Memorial Institute Composition for binding bioactive substances
EP0116361A2 (en) 1983-02-07 1984-08-22 Fuji Photo Film Co., Ltd. Analytical element for dry analysis
US4472494A (en) * 1980-09-15 1984-09-18 Napp Systems (Usa), Inc. Bilayer photosensitive imaging article
DE3602486A1 (en) 1986-01-29 1987-07-30 Sanyo Kokusaku Pulp Co METHOD FOR PRODUCING A COLOR FILTER
EP0246602A2 (en) 1986-05-20 1987-11-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Device having a thin film of a polymer
EP0286118A2 (en) 1987-04-09 1988-10-12 Nova Biomedical Corporation Glucose electrode and method of determining glucose
JPH01241541A (en) * 1988-03-23 1989-09-26 Nippon Kayaku Co Ltd Colored pattern forming method
DD275538A1 (en) 1988-09-12 1990-01-24 Feutron Greiz Veb METHOD FOR PRODUCING A CAPACITIVE SORPTION HUMID SENSOR
US4923948A (en) * 1987-09-24 1990-05-08 Japan Synthetic Rubber Co., Ltd. Curable composition
US4943512A (en) * 1987-11-12 1990-07-24 Chisso Corporation Photocurable and dyeable resin composition with bisazide and dyeable acrylic copolymer
US4960722A (en) * 1985-08-29 1990-10-02 Matsushita Electric Industrial Co., Ltd. Sensor using a field effect transistor and method of fabricating the same
US5041570A (en) * 1988-08-03 1991-08-20 Toyo Gosei Kogyo Co., Ltd. Photosensitive 4,4'-diazidostilbene derivative
US5053225A (en) * 1988-03-18 1991-10-01 Fuji Photo Film Co., Ltd. Functional organic thin film chemically bonded to biologically active agent
DD298268A5 (en) 1989-03-02 1992-02-13 Zentralinstitut Fuer Molekularbiologie,De PROCESS FOR IMMOBILIZING BIOLOGICAL ACTIVE MATERIALS
US5154808A (en) * 1987-06-26 1992-10-13 Fuji Photo Film Co., Ltd. Functional organic thin film and process for producing the same
US5157018A (en) * 1984-06-08 1992-10-20 Hoechst Aktiengesellschaft Perfluoroalkyl group-containing polymers and reproduction layers produced therefrom
US5202227A (en) * 1989-06-03 1993-04-13 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Control of cell arrangement
WO1994028414A1 (en) 1993-05-29 1994-12-08 Cambridge Life Sciences Plc Sensors based on polymer transformation
US5411836A (en) * 1990-08-14 1995-05-02 Nippon Oil Co., Ltd. Positive type photoresist composition comprising a polymer having carbon-carbon double bonds with a maleic half ester and a maleimide attached to the backbone
US5725978A (en) * 1995-01-31 1998-03-10 Basf Aktiengesellschaft Water-soluble photosensitive resin composition and a method of forming black matrix patterns using the same
US5846814A (en) 1996-02-27 1998-12-08 Bayer Aktiengesllschaft Solid-supported membrane biosensors
US6020093A (en) * 1998-05-13 2000-02-01 Toyo Gosei Kogyo, Ltd. Photosensitive compounds, photosensitive resin compositions, and pattern formation method making use of the compounds or compositions
EP1104883A2 (en) 1992-10-01 2001-06-06 Australian Membrane And Biotechnology Research Institute Improved sensor membranes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT375486B (en) * 1982-12-07 1984-08-10 Philips Nv SYSTEM FOR RECORDING AND / OR EVALUATING TWO MARKING SIGNALS
JPS645489A (en) * 1987-06-26 1989-01-10 Fuji Photo Film Co Ltd Functional organic thin film and production thereof

Patent Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3884703A (en) * 1972-04-17 1975-05-20 Hitachi Ltd Bisazide sensitized photoresistor composition with diacetone acrylamide
FR2245009A1 (en) 1973-09-21 1975-04-18 Kodak Pathe Protein contng photo resist compsn with photoisomerisable cpd - which on exposure has greater enzyme inhibiting power
US4251620A (en) * 1975-02-19 1981-02-17 Fuji Photo Film Co., Ltd. Light-sensitive printing plate process
US4288526A (en) * 1975-02-19 1981-09-08 Fuji Photo Film Co., Ltd. Light-sensitive printing plates with discontinuous over-coating
US4106938A (en) * 1977-05-23 1978-08-15 Eastman Kodak Company Vesicular composition, element and process utilizing a diol
US4472494A (en) * 1980-09-15 1984-09-18 Napp Systems (Usa), Inc. Bilayer photosensitive imaging article
US4451568A (en) * 1981-07-13 1984-05-29 Battelle Memorial Institute Composition for binding bioactive substances
EP0116361A2 (en) 1983-02-07 1984-08-22 Fuji Photo Film Co., Ltd. Analytical element for dry analysis
US5157018A (en) * 1984-06-08 1992-10-20 Hoechst Aktiengesellschaft Perfluoroalkyl group-containing polymers and reproduction layers produced therefrom
US4960722A (en) * 1985-08-29 1990-10-02 Matsushita Electric Industrial Co., Ltd. Sensor using a field effect transistor and method of fabricating the same
DE3602486A1 (en) 1986-01-29 1987-07-30 Sanyo Kokusaku Pulp Co METHOD FOR PRODUCING A COLOR FILTER
EP0246602A2 (en) 1986-05-20 1987-11-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Device having a thin film of a polymer
EP0286118A2 (en) 1987-04-09 1988-10-12 Nova Biomedical Corporation Glucose electrode and method of determining glucose
US5154808A (en) * 1987-06-26 1992-10-13 Fuji Photo Film Co., Ltd. Functional organic thin film and process for producing the same
US4923948A (en) * 1987-09-24 1990-05-08 Japan Synthetic Rubber Co., Ltd. Curable composition
US4943512A (en) * 1987-11-12 1990-07-24 Chisso Corporation Photocurable and dyeable resin composition with bisazide and dyeable acrylic copolymer
US5053225A (en) * 1988-03-18 1991-10-01 Fuji Photo Film Co., Ltd. Functional organic thin film chemically bonded to biologically active agent
JPH01241541A (en) * 1988-03-23 1989-09-26 Nippon Kayaku Co Ltd Colored pattern forming method
US5041570A (en) * 1988-08-03 1991-08-20 Toyo Gosei Kogyo Co., Ltd. Photosensitive 4,4'-diazidostilbene derivative
DD275538A1 (en) 1988-09-12 1990-01-24 Feutron Greiz Veb METHOD FOR PRODUCING A CAPACITIVE SORPTION HUMID SENSOR
DD298268A5 (en) 1989-03-02 1992-02-13 Zentralinstitut Fuer Molekularbiologie,De PROCESS FOR IMMOBILIZING BIOLOGICAL ACTIVE MATERIALS
US5202227A (en) * 1989-06-03 1993-04-13 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Control of cell arrangement
US5593814A (en) * 1989-06-03 1997-01-14 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Control of cell arrangement
US5411836A (en) * 1990-08-14 1995-05-02 Nippon Oil Co., Ltd. Positive type photoresist composition comprising a polymer having carbon-carbon double bonds with a maleic half ester and a maleimide attached to the backbone
EP1104883A2 (en) 1992-10-01 2001-06-06 Australian Membrane And Biotechnology Research Institute Improved sensor membranes
WO1994028414A1 (en) 1993-05-29 1994-12-08 Cambridge Life Sciences Plc Sensors based on polymer transformation
US5725978A (en) * 1995-01-31 1998-03-10 Basf Aktiengesellschaft Water-soluble photosensitive resin composition and a method of forming black matrix patterns using the same
US5846814A (en) 1996-02-27 1998-12-08 Bayer Aktiengesllschaft Solid-supported membrane biosensors
US6020093A (en) * 1998-05-13 2000-02-01 Toyo Gosei Kogyo, Ltd. Photosensitive compounds, photosensitive resin compositions, and pattern formation method making use of the compounds or compositions

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts 107:106351.
Chemical Abstracts 125:45144.
Chemical Abstracts 84:82561.
Feb. 1, 1994 Die Mikrosystemtechnik und ihre Anwendugsgebiete Von Wolfgang Menz Spektrum der Wissenschaft pp. 92-99.
Jan. 1, 1986 Supported planar membranes in studies of cell-cell recognition in the immune system H.M. McConnell et al. Biochimica et Biophysica Acta 864 pp. 95-106.
Kosar, Jaromir, Light-sensitive Systems: Chemistry and Application of Nonsilver Halide Photographic Processes, 1965, pp 276,324, 331,336.* *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060244118A1 (en) * 2001-01-31 2006-11-02 Gentex Corporation High power radiation emitter device and heat dissipating package for electronic components
US7489031B2 (en) * 2001-01-31 2009-02-10 Gentex Corporation High power radiation emitter device and heat dissipating package for electronic components
US20060277778A1 (en) * 2005-06-10 2006-12-14 Mick Stephen E Reusable template for creation of thin films; method of making and using template; and thin films produced from template
US7713053B2 (en) 2005-06-10 2010-05-11 Protochips, Inc. Reusable template for creation of thin films; method of making and using template; and thin films produced from template
US20100221488A1 (en) * 2005-06-10 2010-09-02 Protochips, Inc. Reusable template for creation of thin films; method of making and using template; and thin films produced from template
CN103528866A (en) * 2013-10-18 2014-01-22 江苏蓝拓生物科技有限公司 Preparation method of carbon supporting film
CN103528866B (en) * 2013-10-18 2016-01-20 江苏蓝拓生物科技有限公司 The preparation method of carbon supporting film
WO2021038058A1 (en) 2019-08-30 2021-03-04 Westfaelische Wilhelms-Universitaet Muenster Method for manufacturing a holey film, in particular for electron microscopy applications

Also Published As

Publication number Publication date
DE59712525D1 (en) 2006-01-19
ATE313078T1 (en) 2005-12-15
EP0920618A1 (en) 1999-06-09
JP3624382B2 (en) 2005-03-02
DE19705909A1 (en) 1998-08-20
EP0920618B1 (en) 2005-12-14
WO1998008086A1 (en) 1998-02-26
JP2001501728A (en) 2001-02-06

Similar Documents

Publication Publication Date Title
EP1584981B1 (en) Polymer composite
US5154808A (en) Functional organic thin film and process for producing the same
US5580697A (en) Chemical functionalization of surfaces
US6821692B1 (en) Kind of thin films for microsystem technology and microstructuring and their use
RU2492487C2 (en) Method of obtaining microbeeds and microbeeds
CN1216292C (en) Method for fixing biological macro molecule in common pattern on inorganic silicone material surface
US7608389B2 (en) Photoresists processable under biocompatible conditions for multi-biomolecule patterning
CA2158550A1 (en) Chemical functionalization of polymers
JPH04173841A (en) Method for partially forming polymer membrane having functional group
JPH069699A (en) Immobilization of protein
JP4487069B2 (en) Optical patterning material and optical pattern forming method
JPS62171684A (en) Immobilized glucose oxidase enzyme membrane and production thereof
Wohlfart et al. Application of Thin Cross-Linked Gelatin Layers in Micro Systems Technology
JPS60125841A (en) Positive type photoresist composition
JPS62171685A (en) Immobilized lypase enzyme membrane and production thereof
DE19634120A1 (en) Thin film for microsystem technology and microstructuring
EP0077056A1 (en) Negative-type resist sensitive to ionizing radiation
DOUVAS et al. PHOTOLITHOGRAPHIC MATERIALS FOR NOVEL BIOCOMPATIBLE LIFT OFF PROCESSES
JP2001337458A (en) Photoresist material
JPH023493B2 (en)
JPS63298336A (en) Contrast enhanced material for pattern formation
JPS63167351A (en) Photoresist composition
JPS60235132A (en) Formation of pattern
JPS622252A (en) Pattern formation
JPS58215649A (en) Etching resist

Legal Events

Date Code Title Description
AS Assignment

Owner name: CLONDIAG CHIP TECHNOLOGIES GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ERMANTRAUT, EUGEN;KOEHLER, JOHANN MICHAEL;SCHULZ, TORSTEN;AND OTHERS;REEL/FRAME:010008/0666

Effective date: 19990201

FEPP Fee payment procedure

Free format text: PAT HOLDER NO LONGER CLAIMS SMALL ENTITY STATUS, ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: STOL); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20121123